ISSN 00-58, Kinetics and atalysis, 006, Vol 7, No, pp 70 7 MAIK Nauka /Interperiodica (Russia, 006 riginal Russian Text SG Voronina, A Revkov, AL Perkel, 006, published in Kinetika i Kataliz, 006, Vol 7, No, pp 75 79 Kinetics and Mechanism of the Liquid-Phase xidation of tert-butyl Phenylacetate S G Voronina, A Revkov, and A L Perkel Kuzbass State Technical University, Kemerovo, 65008 Russia Received ctober 8, 00 Abstract The oxidation of tert-butyl phenylacetate in ortho-dichlorobenzene at 0 occurs with short chains The primary nonperoxide reaction products (tert-butyl α-hydroxyphenylacetate, tert-butyl α-oxophenylacetate, and benzaldehyde are formed by the decomposition of a hydroperoxide (tert-butyl α-hydroperoxyphenylacetate and (or by the recombination of peroxy radicals with and without chain termination Benzaldehyde and tert-butyl α-hydroxyphenylacetate undergo radical chain oxidation in a reaction medium to result in benzoic acid and tert-butyl α-oxophenylacetate omolytic hydroperoxide decomposition is responsible for process autoacceleration and results in benzaldehyde, which is also formed from hydroperoxide by a nonradical mechanism, probably, via a dioxetane intermediate Both of the reactions are catalyzed by benzoic acid Benzoic acid has no fect on hydroperoxide conversion into tert-butyl α-oxophenylacetate, which most likely occurs as a result of hydroperoxide decomposition induced by peroxy radicals The rate constants of the main steps of the process and kinetic parameters have been calculated by solving an inverse kinetic problem DI: 0/S00580600 Ester products are widely used as solvents, plasticizers, and lubricating oil components in chemical industry and technology They are formed as by-products in the liquid-phase oxidation reactions of hydrocarbons and their oxygen derivatives [ ] In these reactions, as well as in the course of the thermooxidative decomposition of the above products, esters undergo various oxidative reactions, the specifics of which depend on the presence of an electron-acceptor group This group affects the closest bonds of both acyl and alkoxy molecular fragments [, 5] The presence of several reaction sites in an ester molecule significantly complicates the reaction kinetics; the mechanisms of conversion of intermediate products are difficult to study because the same compounds can often be obtained via several reaction paths Therore, adequately reliable information on the kinetics and mechanisms of the oxidative reactions of esters at α- bonds can be obtained only by studying compounds with specially chosen structures [], such as benzyl benzoate [6], benzyl phenylacetate [7], and tert-butyl phenylacetate [8] In this work, we used tert-butyl phenylacetate in order to study the kinetics and mechanisms of the oxidative decomposition of the ester functional group at the α- bonds of an acyl fragment EXPERIMENTAL tert-butyl phenylacetate was prepared by the acylation of tert-butanol with phenylacetyl chloride in a pyridine medium It was purified by vacuum rectification, bp ë (5 Torr According to GL data, the purity of the substance was no worse than 997 ± 0% ortho-dichlorobenzene was purified in accordance with a previously published procedure [8] The ester was oxidized with air in a bubbler-type glass reactor in the kinetic region of oxygen consumption The temperature was maintained to within ±0 K The total concentration of peroxide compounds was determined by iodometric titration Peroxybenzoic acid was determined by GL from the yields of diphenyl sulfoxide and diphenyl sulfone, the products of diphenyl sulfide oxidation by a peroxy acid [9] The other products were determined by GL The methods used for the identification of reaction products and the conditions of sample treatment and GL separation were reported elsewhere [8] The unknown parameters of rate equations were calculated using a program based on the least-squares method in Delphi 55 A set of differential equations was solved using the fourth-order Runge Kutta method at each particular step RESULTS AND DISUSSIN tert-butyl phenylacetate (a 5 M solution in orthodichlorobenzene was oxidized with air at 0 ë Figure shows the experimental concentrations of reaction products (peroxide compounds (primarily tert-butyl α-hydroperoxyphenylacetate, tert-butyl α-hydroxyphenylacetate, tert-butyl α-oxophenylacetate, benzaldehyde, benzoic acid, and peroxybenzoic acid and the 70
KINETIS AND MEANISM F TE LIQUID-PASE XIDATIN 7 total concentration of reaction products It can be seen in Fig that the first four products began to accumulate simultaneously; then, they were formed in consecutive parallel reactions tert-butyl α-hydroperoxyphenylacetate is the primary molecular product of the radical chain oxidation of tert-butyl phenylacetate: ( +R, ( ( (I At the early stages of oxidation, tert-butyl α-hydroxyphenylacetate, tert-butyl α-oxophenylacetate, and benzaldehyde are primarily formed by the recombination of peroxy radicals with chain termination (by the Russell mechanism and without chain termination [8]: ( k t + (, (II k' ( ( ( (III As tert-butyl α-hydroperoxyphenylacetate was accumulated in the reaction medium, the reaction paths of benzaldehyde and tert-butyl α-oxophenylacetate formation related to hydroperoxide decomposition became important The homolytic reaction path resulted in benzaldehyde rather than tert-butyl α-hydroxyphenylacetate [8]: ( ( ( ne of the probable mechanisms of keto ester formation seems to be the hydroperoxide decomposition induced by free radicals [8] R ( ( (IV (V The presence of benzoic acid among the reaction products and the consecutive buildup of benzoic acid with benzaldehyde suggest that the source of the acid is the oxidation reaction of benzaldehyde, which is formed in reactions (III and (IV The conversion of benzaldehyde into benzoic acid can occur either through peroxybenzoic acid (reaction (VI (indeed, it was detected among the oxidation products or through acylperoxy radicals (reaction (VII [0]: +R, ; (VI (VII KINETIS AND ATALYSIS Vol 7 No 006
7 VRNINA et al The radical chain oxidation of tert-butyl α-hydroxyphenylacetate to form tert-butyl α-oxophenylacetate can also occur: ( +R,, R ( (VIII Thus, the set of reactions that occur in the oxidation of tert-butyl phenylacetate can be represented by the following kinetic scheme: R R R R = + R R k t k p '' k' k p R R R R = R (IX The kinetics of reactions (I (VIII can be described by the following set of equations: k R R = dr [ ] ---------------- k p ( k t 05 0 = [ R] ( w i + [ R] 05 ( 0 + ( + k'/k t ( w i + [ R] ; d[ R] ------------------------ = k p ( k t 05 0 [ R] ( w i + [ R] 05 ( ( k + k [ R]; k Ù k p ' where k p, k p ', and k p '' are the reaction rate constants of chain propagation; k t and k' are the reaction rate constants of the quadratic recombination of peroxy radicals with and without chain termination, respectively; is the rate constant of initiation due to hydroperoxide 0 decomposition; w i is the rate of chain initiation; k and k are the fective rate constants of the steps of scheme (IX; [R], [R], [R R =], [R R ], [R], and [R] are the concentrations (mol/l of tert-butyl phenylacetate, tert-butyl α-hydroperoxyphenylacetate, tert-butyl α-oxophenylacetate, tert-butyl α-hydroxyphenylacetate, benzaldehyde, and benzoic acid, respectively The oxidizability parameter of tert-butyl phenylacedr [ R =] -------------------------------- 0 = k [ R] + 05( w i + [ R] + k p ''( k t 05 R R 0 [ ] ( w i + [ R] 05 ; d( [ R] + [ R] ------------------------------------------------------------- 0 = k [ R] + k'/k t ( w i + [ R] ; d[ R] ------------------------ = k ' 0 [ R] + k'/k t ( w i + [ R] e ' ( k t 05 0 [ R] ( w i + [ R] 05 ; dr [ R ] 0 ------------------------------------- = 05( w i + [ R] k p ''( k t 05 R R 0 [ ] ( w i + [ R] 05 ; ( ( (5 (6 0, mol/l, mol/l 5 d[ R] ---------------------------- = k p ''( k t 05 0 [ R] ( w i + [ R] 05 ; [ R] 0 [ R] = [ R] + [ R R =] + [ R R ] + [ R] +[ R], (7 (8 5 7 0 0 0 60 τ, min Fig Experimental concentrations and calculated curves of ( ester consumption and ( 7 reaction product buildup in an experiment on the oxidation of a 5 M tert-butyl phenylacetate solution in ortho-dichlorobenzene at 0 : ( tert-butyl phenylacetate, ( tert-butyl α-hydroperoxyphenylacetate, ( tert-butyl α-oxophenylacetate, ( benzaldehyde, (5 tert-butyl α-hydroxyphenylacetate, (6 benzoic acid, and (7 peroxybenzoic acid 6 KINETIS AND ATALYSIS Vol 7 No 006
KINETIS AND MEANISM F TE LIQUID-PASE XIDATIN 7 alculated rate constants and kinetic parameters for the oxidation of a 5 M tert-butyl phenylacetate solution in orthodichlorobenzene at 0 Parameter tate, which was determined in the temperature range 00 0 ë, is expressed by the equation [8] logk p ( k t 05 (9 = ( ± 09 ( 9 ± 65 kj/mol/0rt ence, it follows that, at 0, k p (k t 05 = 57 0 l 05 mol 05 s 05 Because hydroperoxide decomposition reactions are generally prone to acid catalysis in accordance with published data [, ], we assumed that the corresponding fective constants can depend on the concentration of benzoic acid: alculated value k, l 05 mol 05 s 05 p ' ( k t 05 06 k, l 05 mol 05 s 05 p "( k t 05 0757 w i 0 0 7, mol l s 95 k'/k t k k 0, s 67 0 + 9 [R] 0 6, s 75 0, s 0 0 + 98 [R] k' 0 k'' 0 * Reaction (IV ** Reaction (X, s * 06 0 + 99 [R], s ** 7 0 + 79 [R] = + '[ R] (0 The table summarizes the constants of Eqs ( (8 and (0 and kinetic parameters obtained by solving an inverse kinetic problem, and Fig shows the calculated curves It can be seen in Fig that the calculated curves adequately describe experimental points (the sum of squares of deviations is 0 A comparison of oxidizability parameters for benzaldehyde and tert-butyl α-hydroxyphenylacetate (see the table with the oxidizability parameter of tert-butyl phenylacetate, which was calculated from Eq (9, indicates that the reactivity of bonds in the first two compounds is much higher than that of the ester This circumstance is consistent with the concept that aldehydes and the α- bonds of alcohols are highly reactive [] The ratio between the reaction rate constants of recombination of the peroxy radicals of tert-butyl phenylacetate without and with chain termination (k'/k t = is somewhat higher than that in the oxidation of this ester at 00 ë (k'/k t = 08 [8] This is likely due to the fact that the role of the former reaction increases with temperature n the assumption that the autoacceleration of the process is related to homolytic hydroperoxide decomposition in reaction (IV, is related to k by the equation = ek, ( where e is the coficient of radical escape from a solvent cage; this coficient is equal to 06 for aromatic solvents [] At [R] = 0, substitution of the obtained value of k = 0 s i (table into Eq ( results in k = 8 0 s, which is only ~0% of the calculated value (see the table This circumstance indicates that, in addition to reaction (IV, a nonradical reaction path of benzaldehyde formation from tert-butyl α-hydroperoxyphenylacetate should exist For example, benzaldehyde can be formed via a dioxetane intermediate that results from the intramolecular nucleophilic addition of the hydroperoxide group at the carbonyl group: (, ( (X It is reasonable to assume that dioxetane intermediates are formed in the nonradical decomposition of α-hydroperoxy ketones and α-hydroxy-α-hydroperoxy ketones [] Benzoic acid, which is formed upon the oxidation of tert-butyl phenylacetate, accelerates the decomposition of tert-butyl α-hydroperoxyphenylacetate by reactions (IV and (X but has no fect on reaction (V (see the table and Fig It is well known [, ] that carboxylic acids accelerate the homolytic decomposition of hydroperoxides in reactions like KINETIS AND ATALYSIS Vol 7 No 006
7 VRNINA et al R + R R R R + + R (XI Benzoic acid has the greatest fect on reaction (X (see the table and Fig In this case, it is evident that acid catalysis is related to the formation of acid hydroperoxide complex The reactivity of this complex toward a nucleophilic attack of a hydroperoxide is higher than that of the free ester (δ + >δ +: R δ + + R R δ + R R (XII It is of importance that benzoic acid has no fect on reaction (V, and this is consistent with the proposed mechanism of keto ester formation k 0, s 0 0 0 60 τ, min Fig Dependence of the fective rate constants of ( initiation reactions in the decomposition of tert-butyl α-hydroperoxyphenylacetate and the ( homolytic and ( nonradical decomposition of tert-butyl α-hydroperoxyphenylacetate to benzaldehyde on the duration of oxidation R REFERENES Denisov, ET, Mitskevich, NI, and Agabekov, VE, Mekhanizm zhidkofaznogo okisleniya kislorodsoderzhashchikh soedinenii (Mechanism of Liquid-Phase xidation of xygen-ontaining ompounds, Minsk: Nauka Tekhnika, 975 Perkel, AL, Voronina, SG, and Freidin, BG, Usp Khim, 99, vol 6, no 9, p 79 Perkel, AL, Buneeva, EI, and Voronina, SG, xid ommun, 000, vol, no, p Perkel, AL and Voronina, SG, Zh Prikl Khim, 999, vol 7, no 9, p 09 5 Martem yanov, VS, Ntekhimiya, 986, vol 6, no 6, p 75 6 Voronina, SG, Perkel, AL, and Freidin, BG, Kinet Katal, 99, vol, no, p 66 7 Voronina, SG, Perkel, AL, and Freidin, BG, Zh Prikl Khim, 99, vol 65, no 9, p 08 8 Voronina, SG, Perkel, AL, and Freidin, BG, Zh Prikl Khim, 99, vol 65, no 9, p 079 9 Perkel, AL, Bogomol nyi, GM, and Voronina, SG, Zh Anal Khim, 99, vol 6, no 7, p 0 Perkel, AL and Bogomol nyi, GM, Zh Prikl Khim, 989, vol 6, no 5, p 00 Denisov, ET, Itogi Nauki Tekh, Ser: Kinet Katal, 98, vol 9 Denisov, ET and Kovalev, GI, kislenie i stabilizatsiya reaktivnykh topliv (xidation and Stabilization of Jet Fuels, Moscow: Khimiya, 98 KINETIS AND ATALYSIS Vol 7 No 006